Oxychlorination of hydrocarbons in the presence of non-halide copper containing catalysts

ABSTRACT

Copperchloride has been employed as a reagent for oxychlorination of hydrocarbons. It has now been found that a non-halide copper compound in combination with a rare earth compound is an excellent oxychlorination catalyst, e.g. a CuCO 3  -- CeO 2  catalyst calcined at 900° C. for 1 hour converted 99 mole % of ethylene fed at a selectivity of 100% to chlorinated products, principally vinyl chloride, ethyl chloride and dichloroethane.

This is a division of application Ser. No. 889,671 filed Dec. 31, 1969,now abandoned.

The present invention relates to a catalyst and process foroxychlorination of hydrocarbons.

This invention is applicable to the chlorination of paraffins, olefins,cycloolefins, acetylenes and aromatics. The term oxychlorination as usedherein refers to a reaction in which the source of chlorine employed forthe chlorination is gaseous hydrogen chloride which is made to give upits chlorine in useful form. Copper chloride with various modifiers hasbeen employed to react with hydrogen chloride to make it give up itschlorine through a series of well known reactions. If it is consideredthat the copper chlorides employed in the prior art oxychlorinations ofhydrocarbons are true reagents rather than catalysts, as is generallyaccepted, then the various chlorides involved in those reactions can berepresented in the following typical reaction

    Cu.sub.2 Cl.sub.2 +1/20.sub.2 →CuO.sup. . CuCl.sub.2 ( 1)

    CuO.sup. . CuCl.sub.2 +2HCl→ 2CuCl.sub.2 + H.sub.2 O (2)

    2cuCl.sub.2 +RH→RCl+ Cu.sub.2 Cl.sub.2 + HCl        (3)

It is recognized that each of these reactions has different thermalrequirements and characteristics from each of the others. The varioussolutions proposed have sought to find a compromise set of conditionsfor these diverse reactions.

The present invention provides a solution to the problems encounteredwith copper chloride by using a novel catalyst system. Briefly stated,one aspect of the present invention is a catalyst for use inoxychlorination of hydrocarbons comprising a non-halide copper componentand a rare earth component. Another aspect of the present invention isan improvement in the process of oxychlorination of hydrocarbons whereinthe improvement comprises using a catayst comprising a non-halide coppercomponent and a rare earth component.

The non-halide copper component can contain other elements in additionto copper, for example, a preferred group of elements is selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, arsenic,tin, lead, iron, chromium, molybdenum, tungsten, vanadium, titanium andmixtures thereof. Suitable copper compounds would include copper oxide,copper sulfate, copper nitrate, copper phosphate, copper arsenate,copper stannate, copper plumbate, copper ferrite, copper chromate,copper molybdate, copper tungstate, copper vanadate and copper titanate.

The rare earth component of the present oxychlorination catalysts actsas a promoter for the copper component. Although it has been found thatthe atomic ratio of rare earth promoter to copper can vary widelywithout detriment to the catalytic effect, a preferred atomic ratio ofrare earth promoter to copper is in the range of about 4 to 0.1:1, andeven more preferred, 2 to 0.5:1. The term rare earth is used in itsusual sense to describe the series often called the lanthanide serieswhich includes La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yband Lu. Compounds of these elements or mixtures thereof can be used asthe promoter component of the catalyst. Suitable compounds would be theoxides, nitrates, sulfates, sulfites, phosphates, chlorides, etc. of therare earth elements, e.g. lanthanum hepta-hydrate chloride, ceriumcarbonate, europium iodide, praseodymium acetate, neodymium chloride,samarium nitrate, europium chloride, gadolinium nitrate hexahydrate,terbium iodide, dysprosium selenate, holmium chloride, erbium nitrate,thulium bromide, ytterbium acetate, lutetium iodide and didymium oxide(Di= didymium is used here to describe a mixture of rare earths, e.g., aDi₂ O₃ is typically 45- 46 percent La₂ O₃, 1- 2 percent CeO₂, 9- 10percent Pr₆ O₁₁, 32- 33 percent Nd₂ O₃, 5- 6 percent Sm₂ O₃, 3- 4percent Gd₂ O₃, 0.4 percent Yb₂ O₃ and 1- 2 percent other rare earths).

The promoted copper catalyst can be prepared by a number of means all ofwhich are conventional, for example, salts of copper and a rare earthpromoter can be coprecipitated, or if insoluble or less solublecompounds are employed the components can be mixed in a slurry andsubsequently dried. The catalyst can be prepared in any of the variousforms known such as extruded pellets, cylinders or spheres, or they canbe precipitated as powders or irregular particles. Alternatively, thecatalyst can be ground or milled to a desired form. Another method ofpreparing the catalyst is to deposit them on to supports or carriers,such as alumina, silica alumina, silica gel, pumice, fire brick, etc.

In addition to the copper and rare earth components, other promoters,activators and stabilizers can be present, for example sulfur andphosphorus, alkali metal salts, e.g. sodium chloride, potassium chlorideand lithium chloride.

The catalysts can be used without further treatment after preparation,however, greater activity and selectivity are noted when the catalystsare activated by heating at elevated temperatures, i.e. 600° - 1100° C.in a controlled atmosphere, e.g. air, nitrogen, helium, etc., for 1/2 -4 hours prior to use.

The feed for the present oxychlorination is a hydrocarbon, for example,methane, ethane, propane, butane, hexane, hepane, octane, decane,ethylene, propylene, butene, pentenes, butadiene-1,2 butadiene-1,3,cyclohexane, cyclooctane, cyclopentene, cyclohexene, cyclopentadiene,ethyl benzene, benzene, allene and the like. Aliphatic hydrocarbons areparticularly suitable for the oxychlorination of the present invention,i.e., paraffin, olefin or acetylene. Generally, the feed will consist ofaliphatic hydrocarbons of 1 to 30 carbons. The process is particularlyuseful for acyclic hydrocarbons having 2 to 12 carbon atoms, preferablyC₂ - C₄.

The products of the present oxychlorinations will be as varied as thestarting materials. The product will for the most part be a mixture ofthe chlorinated analogues of the hydrocarbon feed. Generally, mono anddichloro compounds predominate, however, there are substantial amountsof polychlorides and perchlorides, for example, in the case of an ethanefeed, the products will be ethyl chloride, dichloroethane, vinylchloride, other polychloro ethanes and ethylene. High temperatures areless favorable to chlorination and favor dehydrogenation. In someinstances the mixed product is suitable for use as such, as for example,a general solvent. However, in most cases, it will be desirable toseparate some or all of the various products. This can be achieved in anumber of conventional ways, for example, distillation, fractionalcrystallization, solvent extraction, chromatographic extraction,selective reaction of one or more components or any combination of suchconventional methods.

The oxychlorination reactions are generally carried out at elevatedtemperatures by passing a gaseous stream containing the hydrocarbon,oxygen and HCl through a bed of catalyst although other methods such asa fluidized catalyst bed can be employed, e.g. at 300° to 650° C. Underthese conditions the hydrogen chloride is oxidized to chlorine andwater. Since the reaction is highly exothermic no external applicaton ofheat is generally necessary, although heat may be applied initially tostart the reaction. The particular preferential temperature within thepermissible broad temperature range will vary to some extent with thenature of the catalyst and the hydrocarbon, necessitating somewhathigher or lower temperatures, e.g. 200° - 700° C. than generallyapplicable. In the present process it has been found that chlorine canbe used to replace a portion or all of the hydrogen chloride withsubstantially the same results.

In a continuous process a convenient method of measuring hydrocarbonfeed is in terms of the volume of hydrocarbon which contacts unit volumeof catalyst composition per hour which is in units of reciprocal hours(hr⁻ ¹) and is commonly designated gaseous hourly space velocity (GHSV).The GHSV in the present process can be varied over a wide range of, forexample 25 to 600 GHSV. General indications are that the catalyst of theinvention will give higher conversion at lower rates, i.e. GHSV< 300although some catalyst will exhibit substantially the same results at 50and 400 GHSV. Lower conversions can be offset to some extent by the useof higher temperatures, however, there will normally be a reduction inselectivity to the organic chlorides with increased temperatures. Thus,the final selection of reaction conditions will depend on the value ofhigh throughput to the operator and the degree of selectivity desired orthe degree of non-selectivity that can be tolerated. Normally, thepressure will be atmospheric or somewhat less, however, the pressure canbe adjusted as necessary for the operation of the process as previouslyindicated.

The hydrogen chloride is introduced into the system in substantiallyanhydrous form although it may contain small amounts of water. Theoxygen can be introduced into the reaction zone as relatively pureoxygen or in a mixture such as in air. The mole ratio of oxygen to HClis usually such as to sufficiently liberate the chlorine.Stoichiometrically, this can be derived from the equation:

    4HCl+O.sub.2 = 2Cl.sub.2 +2H.sub.2 O

however, in practice the mole ratio of oxygen to HCl can vary in therange of from 0.1:1 to 3:1. The mole ratio of hydrogen chloride tohydrocarbon will vary over a wide range of from 0.5:1 to 5:1 and morepreferably 0.7:1 to 3:1.

In addition to oxygen, hydrogen chloride and hydrocarbon there can bepresent an inert diluent gas such as helium, argon, nitrogen or steam.When used, the diluent is generally present in a mole ratio of diluentto hydrocarbon in the range of from 0.5:1 to 20:1.

The process of the present invention can be carried out in any of theknown types of conventional reactors, e.g. fixed bed, fluidized bed,Houdry flow, riser type and the like. Among the advantages of thepresent catalysts is high selectivity to the chlorinated hydrocarbonswhich in turn makes the process particularly suited to fixed bedreactors. The relatively low temperatures that can be employed allow theprocess to operate with a minimum of catalyst loss due tovolatilization.

The following examples are presented to further illustrate theinvention. Various methods of analysis and separation of product foridentification were used including vapor phase chromatography, nuclearmagnetic resonance and infrared. The examples were run in a one inchI.D. tubular Vycor* reactor, equipped with an external electric furnace.The reaction conditions and the active materials used are set forth inthe specific examples. The hydrocarbon, oxygen, hydrogen chloride anddiluent, if any, were added at the top of the reactor. The results arereported in mole percent conversion, selectivity and yield of thedesignated product. If not otherwise stated the catalysts were supportedon Vycor rings. The catalysts compositions according to the inventionhave the copper component and a rare earth promoter component present inapproximate equimolar quantities unless otherwise stated.

EXAMPLES 1- 5

These examples demonstrate the basic concept of the invention and showthe improvement of the invention catalysts over the individualcomponents. The conditions and results are set out in Table I. Theresults are set out as ##STR1## for each run at the indicatedtemperatures.

This indicates: ##STR2##

                                      TABLE I                                     __________________________________________________________________________              Feed.sup.1    Conversion/Selectivity/Yield mole %                   Ex-                Molar                                                                              at ° C. Temperature                            ample                                                                             Catalyst                                                                            Composition                                                                            Ratio                                                                              300       350       400       450                     __________________________________________________________________________                                2.5/2.1   6.7/4.6   28/22                         1   CuCO.sub.3                                                                          C.sub.2.sup.= /O.sub.2 /HCl/He                                                         1/0.5/2/2                                                                          83  95/80 69  97/67 80  76/61      --                                             100/83    100/69    99+/80                                                    0.4/0.1   5.5/1.2   16/4.0    34/11               2   CeO.sub.2 on                                                                        C.sub.2.sup.= /O.sub.2 /HCl/He                                                         1/0.5/1/2                                                                          23  99+/23                                                                              22  91/20 25  84/21 33  77/25                   AMC                     99+/23    99/22     98/24     96/32                                                               14/2.9    29/13               3    "    C.sub.2 /O.sub.2 HCl/He                                                                1/1/2/4   --        --   21  75/16 45  62/28                                                               96/20     83/37                                           0.3/0.2   1.5/1.4   1.2/1.0   44/33               4   CuCO.sub.3 .                                                                        C.sub.2.sup.= /O.sub.2 /HCl/He                                                         1/0.5/2/2                                                                          72  99/71 92  92/85 87  72/63 75  55/41                   CeO.sub.2               99+/72    99+/91    99+/86    98/73                                           0.2/0.2   1.0/1.0   1.2/1.2   16/14               5   CuCO.sub.3 .                                                                        C.sub.2.sup.= /O.sub.2 /HCl/He                                                         1/0.5/2/2                                                                          99  99+/98                                                                              99  96/95 96  71/68 85  35/30                   CeO.sub.2               100/99    100/99    99+/96    99/84                   (1 hr at                                                                      900° C)                                                            __________________________________________________________________________     .sup.1 GHSV = 100                                                              C.sub.2.sup.= = ethylene                                                      C.sub.2 = ethane                                                             .sup.2 AMC = 4 to 5 mesh alumina supports, Carborundum Company                .sup.3 activated at 900° C. for 1 hour in air                     

It is readily apparent from Table I that the catalyst compositionsaccording to the present invention are superior to the individualcomponents thereof.

EXAMPLES 6- 8

These examples illustrate the use of a copper compound and a mixture ofrare earth compounds. The conditions and results are reported in TableII. In these examples as well as Examples 9- 19 the items within the {represent in order the mole % (selectivity/yield) of

vinyl chloride

ethyl chloride

dichloroethane

other chlorinated compounds

ethylene (with ethane feed)*

The feed was ethane. The molar ratio of C₂ /O₂ /HC1/He was 1/1/2/4 andGHSV= 100 in each run. Example 8 shows the use of ferric oxide promotedwith the same mixture of rare earth compounds as Example 7. It can beseen that the conversion of Example 8 is not as good as Example 7 andthat the iron catalyst produces a much higher yield of ethyleneby-product.

                                      TABLE II                                    __________________________________________________________________________                 Conversion/Selectivity/Yield, Mole %                                          at Temperature ° C.                                       __________________________________________________________________________    Example                                                                            Catalyst                                                                              300    350    400    450    500    550                           __________________________________________________________________________                           4.0/1.0                                                                              7.5/3.4                                                                              24/22  28/26  25/25                                             77/19  50/23  14/13  8.6/7.9                                                                              4.5/4.5                    6    Didymium.sup.1 25 tr./tr.                                                                           45 5.2/2.3                                                                           90 4.9/5.4                                                                           92 4.6/4.2                                                                           99 2.9/2.9                         Hydrate           8.5/2.1                                                                              12/5.4 37/33  26/24  15/15                                             tr./tr.                                                                              14/6.3 14/13  20/18  33/33                                      15/12         10/9.5 19/19  38/38                                             26/21         13/12  4.5/4.5                                                                              2.2/2.2                           7    [Didym. Hydr.                                                                         82 22/18      95 22/21                                                                             99 15/15                                                                             99 6.3/6.3                                                                               --                             CuCO.sub.3]                                                                              22/18         50/47  51/50  30/30                                  1 hr. at 900°  C..sup.2                                                           5.3/4.3       1.8/1.7                                                                              4.3/4.3                                                                              16/16                                             1.9/0.5                                                                              4.2/1.6                                                                              10/8.3 20/19                                                    1.9/0.5                                                                              65/25  26/22  15/14                                    8    [Didym, Hydr.                                                                         25 10/2.5                                                                            39 5.8/2.3                                                                           83 11/9.1                                                                            96 8.3/8.0                                                                               --     --                             Fe.sub.2 O.sub.3                                                                         5.7/1.4                                                                              18/7.0 31/26  29/28                                         1 hr. at 900° C..sup.2                                                            14/3.5 3.7/1.4                                                                              16/13  19/18                                    __________________________________________________________________________     .sup.1 Didymium - used to represent a mixture of rare earth compounds.        .sup.2 Calcined in air for 1 hour at 900° C.                      

EXAMPLES 9- 13

These examples all use a CuCO₃.sup. . CeO₂ (equimolar) catalyst calcinedin air for 1 hour at 900° C. and a GHSV of 100. The example shows theeffects of varying the molar ratio of reagents and helium diluent. Thefeed was ethane held constant at one molar. The results are shown inTable III and are presented in the same manner as in examples 6- 8.

                                      TABLE III                                   __________________________________________________________________________    Feed              Conversion/Selectivity/Yield, Chromatogr. Mole %                        Molar Temp., ° C.                                          __________________________________________________________________________    Example                                                                            Composition                                                                          Ratio 350    400    450    500    550                             __________________________________________________________________________                                1.0/0.2                                                                              3.3/1.7                                                                              4.8/1.6                                                         61/12  22/11  11/3.7                               9   C.sub.2 /O.sub.2 HCl/He                                                              1/0.25/1/1                                                                              -- 20 32/6.4                                                                            50 34/17                                                                             34 24/8.3  --                                                      5.5/1.1                                                                              32/16  20/6.7                                                          tr./tr.                                                                              3.9/2.0                                                                              32/11                                                    2.4/0.9                                                                              2.0/1.0                                                                              17/7.4 20/8.1                                                   12/4.7 6.1/3.2                                                                              2.5/1.0                                                                              2.8/1.1                             10   "      1/0.25/2/1                                                                          38 50/19                                                                             53 40/21                                                                             44 23/10                                                                             41 26/11   --                                               30/11  41/22  48/21  29/12                                                    tr./tr.                                                                              3.3/1.8                                                                              5.1/2.2                                                                              14/5.9                                                   1.0/0.4                                                                              2.8/2.0                                                                              7.4/6.5                                                                              28/24                                                    45/18  15/11  3.5/3.1                                                                              2.4/2.1                             11   "      1/0.5/2/4                                                                           41 40/16                                                                             72 57/41                                                                             88 47/42                                                                             88 0.8/0.7                                                                               --                                               10/4.1 23/17  29/26  22/20                                                    tr./tr.                                                                              tr./tr.                                                                              7.4/6.5                                                                              41/36                                                    tr./tr.       8/8    5/5                                                      7/21          5/5    1/1                                 12   "      1/1/2/4                                                                             30 21/6    -- 96 25/24                                                           7/2           36/349 25/25   --                                                                    44/44                                                    tr./tr.       6/6    3/3                                                             1.6/0.3                                                                              6.4/5.9                                                                              10/8.3 17/16                                                    77/15  26/24  16/13  4.0/3.7                      13   "      1/1/4/4   -- 19 14/2.7                                                                            92 22/20                                                                             83 16/13                                                                             92 9.4/8.7                                                  6.9/1.3                                                                              36/33  33/27  28/26                                                    tr./tr.                                                                              4.5/4.1                                                                              21/18  8.4/7.7                      __________________________________________________________________________

EXAMPLES 14- 16

These examples demonstrate the effect of varying the GHSV (50, 100, 400)on a particular catalyst and ratio of reagents. The catalyst was aCuCO₃.sup. . CeO₂ (equimolar) calcined in air for 1 hour at 900° C. Themolar ratio of ethane/O₂ /HCl/He was constant at 1/1/2/4 in each run.The results shown in Table IV indicate that for this catalyst and theseratios of reagents GHSV of 100- 300 at 400°- 450° C. would be mostsuitable for the reduction of by-products such as ethylene.

                                      TABLE IV                                    __________________________________________________________________________             Conversion/Selectivity/Yield, Chromatogr. mole %                              Temp. ° C.                                                    __________________________________________________________________________    Example                                                                            GHSV                                                                              300                                                                              350     400    450    500    550                                  __________________________________________________________________________                    tr./tr.                                                                              6.2/4.0                                                                              11/7.7                                                          64/14  17/11  5.0/3.5                                         14    50 -- 22  36/8.0                                                                            64 51/32                                                                             70 11/7.7  --     --                                               tr./tr.                                                                              16/10  15/12                                                           tr./tr.                                                                              4.9/3.1                                                                              51/36                                                           1.0/0.4                                                                              2.8/2.0                                                                              7.4/6.5                                                                              28/24                                                    45/18  15/11  3.5/3.1                                                                              2.4/2.1                                  15   100 -- 41  40/16                                                                             72 57/41                                                                             88 47/42                                                                             88 0.8/0.7                                                                               --                                               10/4.1 23/17  29/26  22/20                                                    tr./tr.                                                                              tr./tr.                                                                              7.4/6.5                                                                              41/36                                                           tr./tr.                                                                              8.3/4.1                                                                              11/5.6 10/5.2                                                   63/4.1 31/15  24/12  13/6.9                            16   400 --      -- 6.5                                                                              28/1.8                                                                            49 23/11                                                                             51 9.7/4.9                                                                           52 2.1/1.1                                                  9.2/0.6                                                                              12/6.0 10/5.1 3.1/1.6                                                  0/0    24/12  40/20  58/30                             __________________________________________________________________________

EXAMPLES 17- 21

These examples demonstrate a further improvement in the catalystactivity obtained with addition promoters. Example 15 is supplied as acomparison. In example 17.2% by weight of 85% phosphoric acid was addedto a CuCO₃.sup. . CeO₂ (equimolar) catalyst calcined 1 hour at 900° C.in air. Examples 18 and 19 show the use of 10% KCl as a second promoter.The results and conditions are given in Table V.

Example 20 and 21 show surprising results when 10% by weight of graphite(Fisher No. 38 graphite) and 10% by weight PbCO₃, respectively, areadded to the copper-cerium catalyst.

                                      TABLE V                                     __________________________________________________________________________                 Feed          Conversion/Selectivity/Yield, Chromatogr. mole                                %                                                               Compo-                                                                             Molar    Temp., ° C.                                 __________________________________________________________________________    Example                                                                            Catalyst                                                                              sition                                                                             Ratio                                                                              GHSV                                                                              300     350    400    450    500                   __________________________________________________________________________                                          1.0/0.4                                                                              2.8/2.0                                                                              7.4/6.5                                                                              28/24                                                    45/18  15/11  3.5/3.1                                                                              2.4/2.1            15   [CuCO.sub.3 .                                                                         C.sub.2 /O.sub.2 /                                                                 1/1/2/4                                                                            100     --  41 40/16                                                                             72 57/41                                                                             88 47/42                                                                             88 0.8/0.7            control                                                                            CeO.sub.2]                                                                            HCl/He                   10/4.1 23/17  29/26  22/20                   1 hr. at                         tr./tr.                                                                              tr./tr.                                                                              7.4/6.5                                                                              41/36                   900° C.                                                                Copper-                  12/7.6  12/9.1 7.6/6.0                                                                              13/12  20/19                   Cerium Cat.              11/6.9  9.5/7.4                                                                              12/9.6 4.5/4.3                                                                              1.7/1/7            17   and 2% PO.sub.4                                                                       C.sub.2 /O.sub.2 /                                                                 1/1/2/4                                                                            "   64 18/12                                                                              78 18/14                                                                             79 22/17                                                                             94 15/14                                                                             98 7.5/7.3                 heated to                                                                             HCl/He           49/32   52/41  51/41  58/57  47/46                   700° Cw/Feed      2.4/1.5 2.2/1.7                                                                              tr./tr.                                                                              2.0/2.0                                                                              5.8/5.7                 Copper-                  0/0     1.1/0.6                                                                              6.9/5.9                                                                              2.4/2.4                                                                              16/16                   Cerium Cat.              100/7.7 62/37  17/15  3.0/3.0                                                                              0.4/0.4            18   and 10% KCl                                                                           C.sub.2 /O.sub.2 /                                                                 "    "   7.7                                                                              0/0  59 17/10                                                                             86 18/16                                                                             99 13/13                                                                             99 9.7/9.6                         HCl/He           0/0     13/7.9 46/39  70/69  47/46                                            0/0     0/0    3.4/2.9                                                                              0.4/0.4                                                                              5.4/5.4                                          tr./tr. 1.7/1.7                                                                              12/11  17/16  32/24                                            0/0     0/0    0/0    0/0    0/0                19     "     C.sub.2 .sup.= /O.sub.2 /                                                          1/0.5/2/2                                                                          "   53 97/51                                                                              99 84/83                                                                             98 46/45                                                                             97 24/23                                                                             75 6.0/4.5                         HCl/He           3.0/1.6 1.3/1.3                                                                              38/37  41/40  37/28                   [CuCO.sub.3 .            1.4/1.3        2.6/2.6                                                                              28/20  29/17                   CeO.sub.2]               1.7/1.6        0.2/0.2                                                                              0.30/0.2                                                                             0.5/0.3            20   1 hr. at 900° C                                                                C.sub.2 .sup.=/O.sub. 2                                                            1/0.5/2/                                                                           "   93 85/79    -- 99 50/49                                                                             70 18/13                                                                             60 4.7/2.8                 + 10% PbCO.sub.3                                                                      HCl . He         10/9.3         45/44  46/32  51/31                   [CuCO.sub.3 .            3.3/2.8 5.4/4.5                                                                              25/21  47/35  66/46                   CeO.sub.2 ]              0.2/0.2 0.2/0.2                                                                              0.5/0.4                                                                              0.7/0.5                                                                              tr./tr.            21   1 hr. at 900° C                                                                C.sub.2 .sup.=/O.sub.2 /                                                           "    "   86 87/75                                                                              84 75/63                                                                             85 38/32                                                                             74 6.4/4.7                                                                           70 tr./tr.                 +10% Fisher                                                                           HCl.sub.2 . He   9.0/7.7 19/16  34/29  40/30  21/15                   No. 38 Graphite                                                          __________________________________________________________________________

EXAMPLES 22-24

These examples show substantial variation of the molar ratio of coppercomponent to rare earth component within the ranges previously reciteddoes not have a substantial effect on the operation of the catalyst. Thefeed was butadiene (BD) principally the 1,3 isomers at a molar ratio ofBD/O₂ /HCl/He of 1/0.5/2/2 and GHSV of 100. The catalyst was CuCO₃.sup..CeO₂. Each catalyst was calcined at 900° C. for 1 hour in air. The molarratio of components is shown in the formulas in Table VI. The resultsare reported as before, i.e. conversion/selectivity/yield with theproducts being in order

dichlorobutadiene

chlorobutene

chlorobutadiene

                                      TABLE VI                                    __________________________________________________________________________                   Conversion/Selectivity/Yield, Chromatogr. mole %                              Temp. ° C.                                              __________________________________________________________________________    Example                                                                            Catalyst  200   250    300    350    400                                 __________________________________________________________________________                                   27/5   34/21  20/11                            22   [CuCO.sub.3 . CeO.sub.2]                                                                    --    -- 58 9/2 62 11/7                                                                              56 8/5                                   1 hr. at 900° C.   47/27  39/24  26/15                                              0/0   30/19  38/25  33/20                                   23   [2CuCO.sub.3 . CeO.sub.2]                                                               5  0/0                                                                              63 12/8                                                                              65 14/9                                                                              61 13/8   --                                    1 hr. at 900° C.                                                                    47/2  49/31  42/27  42/26                                                           25/13  32/20  35/20  38/19                            24   [CuCO.sub.3 . 2CeO.sub.2]                                                                   --                                                                              52 10/5                                                                              62 12/7                                                                              58 14/8                                                                              50 15/8                                  1 hr. at 900° C.                                                                          61/32  49/30  44/25  34/17                            __________________________________________________________________________

EXAMPLES 25- 28

These examples demonstrate a further improvement in the chlorination ofbutadiene when a secondary promoter is present. The same conditions asin Examples 22-24 were employed. The results are also reported as inExamples 22- 24 in Table VII.

                                      TABLE VII                                   __________________________________________________________________________                    Conversion/Selectivity/Yield, Chromatogr. mole %                              Temp. ° C.                                             __________________________________________________________________________    Example                                                                            Catalyst   200                                                                              250    300    350    400                                   __________________________________________________________________________                                 27/5   34/21  20/11                              22   [CuCO.sub.3 . CeO.sub.2]                                                                 --     -- 58 9/2 62 11/7                                                                              56 8/5                                     1 hr. at 900° C. 47/27  39/24  26/15                                                    0/0    26/17  36/23  32/13                              25   [CuCO.sub.3 . CeO.sub.2]                                                                 -- 9  0/0 67 10/7                                                                              63 13/8                                                                              41 13/5                                    1 hr. at 900° C.                                                                        49/4   50/34  41/26  29/12                                   + 10% LiCl                                                                                     16/4   33/22  38/24  35/15                              26   [CuCO.sub.3 . CeO.sub.2]                                                                 -- 27 5/1 67 11/7                                                                              63 13/8                                                                              44 13/6                                    1 hr. at 900° C.                                                                        52/14  46/31  41/26  28/12                                   + 10 % NaCl                                                                   [CuCO.sub.3 . CeO.sub.2]                                                               0/0     44/32  42/30  49/34                                     27   1 hr. at 900° C.                                                                19 0/0                                                                             72 14/10                                                                             72 14/10                                                                             69 16/11   --                                     + 10% KCl                                                                              35/7    36/26  38/27  32/22                                          [CuCO.sub.3 . CeO.sub.2]                                                                       48/34  52/43  51/44                                     28   1 hr. at 900° C.                                                                  -- 71 16/11                                                                             82 16/13                                                                             86 16/14   --                                     + 10% HgCl       33/23  24/20  27/23                                     __________________________________________________________________________

EXAMPLES 29- 32

The molar ratio in the components of the feed was varied in relation tothe butadiene. The GHSV was 100 in each run. Examples 29 and 30 had 1%KCl as addition promoter. A most noteworthy result is found in Examples31 at 300° C. wherein there was a conversion of 90% and a yield of 51mole % dichlorobutadiene. The variables and results are shown in TableVIII. The results are reported as in Examples 22- 24.

                                      TABLE VIII                                  __________________________________________________________________________                Feed     Conversion/Selectivity/Yield, Chromatogr. mole %         Ex-         Compo-                                                                             Molar                                                                             Temp., ° C.                                       ample                                                                             Catalyst                                                                              sition                                                                             Ratio                                                                             200    250    300    350    400    450                   __________________________________________________________________________    22  [CuCO.sub.3 . CeO.sub.2]          27/5   34/21  20/11                     control                                                                           1 hr. at 900° C.                                                               BD/O.sub.2 /                                                                       1/0.5/  --     -- 58 9/2 62 11/7                                                                              56 8/5     --                            HCl/He                                                                             2/2                  47/27  39/24  26/15                                                           12/4   28/16  24/11                     29  "       BD/O.sub.2                                                                         1/0.5/  --     -- 30 5/2 56 9/5 47 9/4     --                            HCl/He                                                                              2/10                56/17  55/31  53/25                                             0/0    14/7          37/29  32/21  23/11              30  "       BD/O.sub.2                                                                         1/0.5/                                                                            10 0/0 53 4/2     -- 78 13/10                                                                             67 11/7                                                                              48 9/4                    + 1% KCl                                                                              HCl/He                                                                             2/10   5/0.5  65/34         45/35  52/35  48/23                                      10/7                        23/16  29/20              31  "       BD/O.sub.2                                                                         1/2/                                                                              65 4/3     --     --     -- 69 10/7                                                                              69 11/8                           HCl/He                                                                             2/4    15/10                       21/15  19/13                                             54/30  57/51  42/37  45/38                     32  "       BD/O.sub.2                                                                         1/1/    -- 56 19/11                                                                             90 21/19                                                                             87 15/13                                                                             85 18/15   --                            HCl/He                                                                             2/4           19/11  15/13  36/31  27/23                     __________________________________________________________________________

EXAMPLES 33- 35

These examples demonstrate the very excellent results obtainable withsteam as the diluent. The conditions and results (reported as inExamples 22-24) are set out in Table IX.

                                      TABLE IX                                    __________________________________________________________________________                Fe            Conversion/Selectivity/Yield, Chromatogr. mole                                %                                                   Ex-         Compo-                                                                             Molar    Temp. ° C.                                   ample                                                                             Catalyst                                                                              sition                                                                             Ratio                                                                             GHSV 200                                                                              250                                                                              300                                                                              350    400    450    500                   __________________________________________________________________________                                          41/31  42/34  38/30                     33  CuCO.sub.3 . CeO.sub.2                                                                BD/O.sub.2 /                                                                       1/0.5/2/7                                                                          100 -- -- -- 76 17/13                                                                             82 15/12                                                                             79 15/12   --                    1 hr. at 900 ° C.                                                              HCl/H.sub.2 O             27/20  36/27  39/31                                                           41/23  43/32  48/39  38/28              34  "       BD/O.sub.2 /                                                                       1/1/4/7                                                                            125 -- -- -- 56 15/8                                                                              75 20/15                                                                             81 20/16                                                                             73 17/12                          HCl/H.sub.2 O             26/11  23/17  24/19  34/25                                                           46/27  49/35  49/31              35  "       BD/O.sub.2 /                                                                       1/1/4/14                                                                           "   -- -- --     -- 58 20/12                                                                             72 4/17                                                                              63 22/13                          HCl/H.sub.2 O                    24/14  21/15  23/14              __________________________________________________________________________

EXAMPLES 36 and 37

These examples are provided to show that the diluent is not necessaryfor the successful operation of the oxychlorination using the presentcatalysts. Example 22 is supplied as a control. The GHSV was 100 foreach run. The other conditions and results are reported in Table X.

                                      TABLE X                                     __________________________________________________________________________                 Feed          *Conversion/Selectivity/Yield, Chrom.                           Compo-                                                                             Molar    Temp., ° C. mol %                           Example                                                                            Catalyst                                                                              sition                                                                             Ratio                                                                              GHSV                                                                              250    300    350    400    450                    __________________________________________________________________________    22   [CuCO.sub.3 . CeO.sub.2]        27/5   34/21  20/11                      control                                                                            1 hr. at 900° C.                                                               BD/O.sub.2 /                                                                       1/0.5/2/2                                                                          100     -- 58 9/2 62 11/7                                                                              56 8/5     --                              HCl/He                  47/27  39/24  26/15                                                    40/8.8 46/36  45/31  45/31  38/26               36   [CuCO.sub.3 . CeO.sub.2 ]                                                             BD/O.sub.2 /                                                                       1/1/4/0                                                                            "   22 12/26                                                                             78 17/13                                                                             69 18/12                                                                             68 17/12                                                                             68 16/11                    1 hr. at 900° C.                                                               HCl/He           23.5/1 24/19  24/17  28/19  28.19                                                    49/35  45/30                             37   [CuCO.sub.3 . CeO.sub.2]                                                              BD/O.sub.2 /                                                                       1/0.5/4/0                                                                          "       -- 72 17/12                                                                             67 17/11   --     --                      1 hr. at 900 ° C.                                                              HCl/He                  26/19  26/17                                  + 5% KCl                                                                 __________________________________________________________________________     *Selectivities and yields to dichlorobutadiene-1,3, chlorobutenes and         monochlorobutadiene-1,3, respectively. (top to bottom).                  

EXAMPLES 38 and 39

Examples 38 and 39 show the oxychlorination of butene-1 and butene-2respectively. The catalyst (equimolar CuCO₃ and CeO₃ calcined 1 hr. at900° C. in air) and 5% KCl secondary promoter were deposited on 4- 5mesh alumina supports (AMC - Carborundum Company). The GHSV was 100 ineach run and the ratio of hydrocarbon/O₂ /HCl/He in each run was1/0.5/2/2. The results are shown in Table XI.

                                      TABLE XI                                    __________________________________________________________________________                                  Conversion/Selectivity                                                        Yield, Chromatogr.                                             Hydrocarbon    Temp. ° C. mole %                        Examples                                                                           Catalyst  Feed   Products*                                                                             450    500                                      __________________________________________________________________________         [CuCO.sub.3 . CeO.sub.2]                                                                       1-ClBD-1,3 11/4.2                                       38   1 hr. at 900° C.                                                                 Butene-1                                                                             2-ClBD-1,3 4.2/1.6  --                                       + 5% KCl on AMC  UNKNOWN 38 40/15                                                              1,3 DiClBa 16/6.1                                                             Other C.sub.n --Cl's                                                                     24/9.1                                                             1-ClBD-1,3 10/4.1  33/17                                                      2-ClBD-1,3 3.2/1.3 1.5/0.8                              39   "         Butene-2                                                                             UNKNOWN 41 34/14                                                                             53  35/19                                                      1,3 DiClBa 13/5.3  18/9.5                                                     Other C.sub.n --Cl's                                                                     37/15   6.0/3.2                              __________________________________________________________________________     *1 - Cl Bd-1,3 = 1-chlorobutadiene-1,3                                         2 - Cl BD-1,3 = 2-chlorobutadiene-1,3                                         1,3 DiClBa = 1,3-dichlorobutanes                                        

EXAMPLE 40

This example demonstrates the operation of the process using chlorinesubstitute for HCl. This run is the same as Example 38 except for thissubstitution. The results are shown in TAble XII. The results show arather constant conversion, selectivity and yield over the temperaturerange of 150° - 350° C.

                                      TABLE XII                                   __________________________________________________________________________    OXYCHLORINATION OF BUTENE-1 AND BUTENE-2                                      CHLORINE VS. HYDROGEN CHLORIDE                                                __________________________________________________________________________              Feed                                                                              Mo-                                                             Ex-       Com-                                                                              lar           Conversion/Selectivity/Yield, Chromatogr.         am-       posi-                                                                             Ra-           Temp. ° C. mole %                          ple                                                                              Catalyst                                                                             tion                                                                              tio                                                                              GHSV                                                                              Products                                                                             150    200    250    300    350                   __________________________________________________________________________       [CuCO.sub.3 .                                                                        Bu-1/      *1,3-DiClBa                                                                             1.4/1.0                                                                              1.4/1.8                                                                              1.5/1.0                                                                              12/8.4 1.1/0.8               CeO.sub.2 ] 1 hr.                                                                    O.sub.2 /                                                                         1/ 100  1,2-DiClBa                                                                             97/68  95/70  93/61  71/50  81/56              40 at 900° C.                                                                    Cl.sub.2 /                                                                        0.5/    2,3-DiClBa                                                                          70 0.1/0.1                                                                           70 tr./tr.                                                                           66 tr./tr.                                                                           70 tr./tr.                                                                           69 0.2/0.1               + 5% KCl                                                                             He  1/2     2-ClBD-1,3                                                                             1.1/0.8                                                                              1.8/1.3                                                                              2.1/1.4                                                                              1.4/1.0                                                                              0.5/0.8               on AMC             Other    0.1/0.1                                                                              2.1/1.5                                                                              2.9/1.9                                                                              3.0/2.1                                                                              6.2/4.3                                  C.sub.n --Cl's                                          __________________________________________________________________________     *1,3-DiClBa = 1,3-dichlorobutane                                               1,2-DiClBa = 1,2-dichlorobutane                                               2,3-DiClBa = 2,3-dichlorobutane                                               2-ClBD-1,3 = 2-chlorobutadiene                                          

No details of catalyst preparation have been given since the proceduresinvolved require the preparation of an aqueous solution or slurry whichis deposited onto the Vycor rings, which are then dried. Some of thecatalysts are calcined as indicated prior to deposition, if any, on thesupports. In any event, these procedures are routine to those in the artand form no part of the invention per se.

The invention claimed is:
 1. An oxychlorination catalyst compositioncalcined at 600° to 1100° C. and consisting of a non-halide coppercomponent of copper and an element selected from the group consisting ofO, S, N, P, As, Pb, Fe, Cr, Mo, W, V, Ti and mixtures thereof and a rareearth compound, said rare earth being selected from the group consistingof La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu andmixtures thereof and the atomic ratio of rare earth to copper being inthe range of 4 to 0.1:1.
 2. The catalyst composition according to claim1 wherein said non-halide copper component is copper oxide, coppersulfate, copper, nitrate, copper phosphate, copper arsenate, copperstannate, copper plumbate, copper ferrite, copper chromite, coppermolyubdate, copper tungstate, copper vanadate or copper titanate.
 3. Thecatalyst composition according to claim 1 wherein the atomic ratio ofrare earth to copper is in the range of about 4 to 0.1:1.
 4. Thecatalyst composition according to claim 3 wherein the atomic ratio ofrare earth to copper is in the range of 2 to 0.5:1.
 5. The catalystcomposition according to claim 1 wherein the rare earth is selected fromthe group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu Gd, Tb, Dy, Ho, Er,Tm, Yb, Lu and mixtures thereof.
 6. The catalyst composition accordingto claim 1 wherein the rare earth is cerium.
 7. The catalyst compositionaccording to claim 6 wherein the rare earth compound is cerium oxide. 8.The catalyst composition according to claim 7 wherein copper componentis copper oxide.
 9. The catalyst composition according to claim 1wherein the rare earth compound is a mixture of rare earths.